EP3931282B1 - Hmpsa incorporating a plasticiser made from a renewable raw material - Google Patents

Description

The subject of the present invention is a hot-melt pressure-sensitive adhesive composition (or HMPSA) as well as a multilayer system which comprises a layer constituted by said composition and which is suitable for the manufacture of self-adhesive articles, in particular labels self-adhesive.

Pressure-sensitive adhesives (also called self-adhesive glues or else, in English, “Pressure Sensitive Adhesives” or PSA) are substances which give the support layer which is coated with them an immediate adhesive power at room temperature. Often referred to by the English term "tack" or even sometimes by the term "tackiness", this immediate tackiness allows the instantaneous adhesion of said self-adhesive support to all kinds of substrates, under the effect of light pressure. and brief. PSAs are widely used for the manufacture of self-adhesive labels which are attached to articles (e.g. packaging) for the purpose of presenting information (such as barcode, denomination, price) and/or for decorative. PSAs are also used for the manufacture of self-adhesive tapes for various uses. Mention may be made, for example, in addition to the transparent adhesive tape widely used in everyday life: the shaping and assembly of cardboard packaging; the protection of surfaces for painting work, in construction; the maintenance of electric cables in the transport industry; the bonding of carpets with double-sided adhesive tape.

The PSAs are generally applied, by continuous coating processes implemented by industrialists called "coaters", over the entire surface of a support layer, where appropriate printable, of large dimensions, at a rate of a quantity (generally expressed in g/m ² ) and designated hereinafter by the term "grammage". The support layer is generally made of paper or film of a single or multi-layered polymeric material. The layer of adhesive composition which covers the support layer is itself covered with a protective non-stick layer (often referred to by the English name “release liner”), which often consists of a silicone film. The multilayer system obtained is generally packaged by winding in the form of large coils (or rolls) up to 2 m wide and 1 m in diameter, which can be stored and transported, such packaging often being referred to as "roll stock".

This multilayer system can be subsequently converted into applicable self-adhesive labels by a label manufacturer called a "converter" (or sometimes by the English name "converter"), by means of conversion processes which include the printing of the information elements and / or decorative desired on the printable face of the support layer, then cut to the desired shape and dimensions.

The protective release layer can be easily removed without modifying the adhesive layer which remains attached to the printable support layer. After separation from its protective non-stick layer, the label is generally applied at a temperature close to ambient temperature on the article (for example the packaging) to be coated either manually or using labeling machines on automated packaging lines.

This multilayer system can also be transformed into self-adhesive tapes by cutting and packaging in rolls of determined width and length.

PSAs advantageously allow, because of their high tack at room temperature, rapid gripping or hanging of the label and/or self-adhesive tape on the substrate (or article) to be coated (for example, in the case of labels, on packaging or, in the case of ribbons, on packaging cartons to be shaped), suitable for obtaining high industrial production rates.

Hot melt adhesives (often referred to as "Hot Melt adhesives" or HM) are substances that are solid at room temperature and contain neither water nor solvent. They are applied in the molten state and solidify on cooling, thus forming a joint which, due to its adhesive power, ensures the fixing of the substrates to be assembled. Some Hot Melts are formulated in such a way as to give the support coated with them a relatively hard and tack-free character. Other Hot Melts provide the support with a relatively soft character and significant tack: these are PSAs which are widely used for the manufacture of self-adhesive articles (for example self-adhesive labels). The corresponding adhesives are designated by the name of “pressure-sensitive hot melt adhesives” or else, in English, by that of “Hot Melt Pressure Sensitive Adhesive” (or “HMPSA”). They therefore also make it possible, because of their adhesive power, to securely attach the label or the tape to the desired substrate, whether it is for example the packaging to be labeled or the cardboard to be assembled.

HMPSAs generally comprise a thermoplastic polymer (particularly a styrenic block copolymer) in combination with tackifying resins and plasticizers.

We know, for example from international applications WO 2008/077509 and WO 2008/110685 , such HMPSA compositions and multilayer systems which comprise an adhesive layer made of said composition, as well as an adjacent printable support layer and protective layer.

The plasticizers which are used in these HMPSA compositions, and in particular those disclosed by these last 2 applications, are generally hydrocarbon oils which are derived from crude petroleum and which are of paraffinic, aromatic and/or naphthenic nature. Such plasticizers are, for example, marketed under the name ^Primol® 352 by the company ExxonMobil, ^Nyflex® 222B or ^Nyflex® 223 by the company Nynas.

However, in the current context of the development of a "green" chemistry, we are increasingly seeking to free ourselves, or at least to reduce the share, of non-renewable raw materials, of oil or fossil origin, at the profit from renewable raw materials, in particular of vegetable origin.

There is therefore a need to replace the plasticizers of petroleum origin used in the HMPSA compositions with plasticizers obtained from renewable raw materials.

The international request WO 99/13016 describes hot-melt compositions which contain, as a plasticizer, a hydrogenated or non-hydrogenated natural oil comprising fatty acids containing from 6 to 22 carbon atoms. Preferred fatty acids are mixtures of C10-C14 carbon atoms, such as coconut oil and mixtures of C18 such as soybean and sunflower oil. These hot-melt compositions are used in a process for bonding a substrate based on fabric or nonwoven to other substrates, with a view to manufacturing a disposable absorbent product, such as for example disposable diapers. However, this document in no way teaches or suggests an HMPSA composition possessing the properties of adhesive power and tack required for its implementation in a multilayer system suitable for the manufacture of self-adhesive articles.

An object of the present invention is to propose on the one hand a new HMPSA composition whose plasticizer is made from renewable raw materials, and on the other hand a multilayer system comprising an adhesive layer consisting of said composition, which are suitable for the manufacture of self-adhesive articles, in particular self-adhesive labels.

Another object of the present invention is to provide an HMPSA composition suitable for forming the adhesive layer of a multilayer system which also has an appropriate adhesive power on different substrates, and even improved.

Another object of the present invention is to provide an HMPSA composition suitable for forming the adhesive layer of a multilayer system which also exhibits suitable tack on different substrates, and even improved.

It has now been found that these objects can be achieved in whole or in part by means of the HMPSA composition and the multilayer system of which the adhesive layer is made up thereof, as described below.

• de 20 à 50 % en poids d'une composition (a1) de copolymères à bloc styrénique qui comprennent au moins un bloc élastomère ;
• de 35 à 65 % en poids d'une ou plusieurs résines tackifiantes (a2) ; et
• de 7 à 25 % en poids d'un plastifiant (a3) ;

caractérisée en ce que le plastifiant (a3) est constitué d'une composition (a3) comprenant une standolie (a3-1) d'une huile végétale.The subject of the present invention is therefore in the first place an HMPSA composition which comprises, on the basis of the total weight of said composition:

• from 20 to 50% by weight of a composition (a1) of styrenic block copolymers which comprise at least one elastomer block;
• from 35 to 65% by weight of one or more tackifying resins (a2); and
• from 7 to 25% by weight of a plasticizer (a3);

characterized in that the plasticizer (a3) consists of a composition (a3) comprising a stand oil (a3-1) of a vegetable oil.

Said HMPSA composition, in addition to its reduced content of non-renewable raw materials due to the use for the plasticizer of a derivative of vegetable oil, is entirely suitable for its implementation in a multilayer system suitable for the manufacture of self-adhesive articles, and especially for the manufacture of self-adhesive labels, because of its adhesive power and its tack.

In fact, said HMPSA composition makes it possible to obtain an adhesive power (also called "pelage" or "peel"), measured according to the FINAT test method no. 1, which is advantageously greater than 5 N/2.54 cm for metallic or polymeric substrates, and greater than 3 N/2.54 cm for cardboard substrates. The HMPSA composition according to the invention also makes it possible to obtain a tack, measured according to the so-called instant adhesion test of the loop described in the FINAT test method no. 9, which is advantageously greater than 10 N/2, 54 cm on glass substrates greater than 8 N/2.54 cm on polymeric substrates and greater than 3 N/2.54 cm on cardboard substrates.

In addition, both the adhesive power and the tack are, surprisingly, greatly improved compared with those of HMPSA compositions in which the plasticizer is a vegetable oil such as sunflower, rapeseed, linseed or soybean oil.

Composition (a1) of styrenic block copolymers :

The HMPSA composition comprises from 20 to 50% by weight of a composition (a1) of styrene block copolymers which comprise at least one elastomer block.

Said styrenic block copolymers have a weight-average molar mass Mw generally comprised between 50 kDa and 500 kDa. They consist of blocks of different polymerized monomers including at least one polystyrene (or styrenic) block, and are prepared by radical polymerization techniques.

Unless otherwise indicated, the weight-average molar masses M _w which are given in this text are expressed in daltons (Da) and are determined by Gel Permeation Chromatography, the column being calibrated with polystyrene standards .

• de 30 à 90 % en poids d'au moins un copolymère dibloc choisi dans le groupe comprenant les SI, SIB, SB, SEB, et SEP, et
• de 10 à 70 % en poids d'au moins un copolymère tribloc choisi dans le groupe comprenant les SIS, SIBS, SBS, SEBS et SEPS ;

la teneur en motifs styréniques totale de ladite composition (a1) variant de 10 à 40 % en poids sur la base du poids total de (a1).According to a preferred embodiment, said composition (a1) consists, on the basis of its total weight:

• from 30 to 90% by weight of at least one diblock copolymer chosen from the group comprising SI, SIB, SB, SEB, and SEP, and
• from 10 to 70% by weight of at least one triblock copolymer chosen from the group comprising SIS, SIBS, SBS, SEBS and SEPS;

the total styrene unit content of said composition (a1) varying from 10 to 40% by weight based on the total weight of (a1).

Triblock copolymers include 2 polystyrene blocks and an elastomer block. They can have various structures: linear, star (also called radial), branched or even comb. Diblock copolymers include 1 polystyrene block and 1 elastomer block.

• A représente un bloc non élastomère styrénique (ou polystyrène), et
• B représente un bloc élastomère qui peut être :
  • le polyisoprène. Le copolymère bloc a alors pour structure : polystyrène-polyisoprène-polystyrène, et pour dénomination : SIS ;
  • le polyisoprène suivi d'un bloc polybutadiène. Le copolymère bloc a alors pour structure : polystyrène-polyisoprène-polybutadiène-polystyrène, et pour dénomination : SIBS
  • le polybutadiène. Le copolymère bloc a alors pour structure : polystyrène- polybutadiène- polystyrène, et pour dénomination : SBS ;
  • le polybutadiène hydrogéné totalement ou en partie. Le copolymère bloc a alors pour structure: polystyrène-poly(éthylènebutylène)- polystyrène et pour dénomination : SEBS ;
  • le polyisoprène hydrogéné totalement ou en partie. Le copolymère bloc a alors pour structure : polystyrène-poly(éthylènepropylène)- polystyrène et pour dénomination : SEPS.

Tri-block copolymers have the general formula:

ABA (I)

in which :

• A represents a non-elastomeric styrene (or polystyrene) block, and
• B represents an elastomer block which can be:
  • polyisoprene. The block copolymer then has the structure: polystyrene-polyisoprene-polystyrene, and the name: SIS;
  • polyisoprene followed by a polybutadiene block. The block copolymer then has the structure: polystyrene-polyisoprene-polybutadiene-polystyrene, and the name: SIBS
  • polybutadiene. The block copolymer then has the structure: polystyrene-polybutadiene-polystyrene, and the name: SBS;
  • totally or partially hydrogenated polybutadiene. The block copolymer then has the structure: polystyrene-poly(ethylenebutylene)-polystyrene and the name: SEBS;
  • fully or partially hydrogenated polyisoprene. The block copolymer then has the structure: polystyrene-poly(ethylenepropylene)-polystyrene and the name: SEPS.

Di-block copolymers have the general formula:

AB(II)

in which A and B are as previously defined.

When the composition (a1) comprises several triblock styrenic copolymers, the latter being chosen from the group comprising SIS, SBS, SEPS, SIBS, SEBS, it is understood that said triblocks can belong to one or more of these 5 families of copolymers. The same is true, mutatis mutandis, for the diblock copolymers.

It is preferred to use a composition (a1) comprising a triblock copolymer and a diblock copolymer having the same elastomer block, in particular because such mixtures are commercially available.

According to a preferred embodiment, the diblock copolymer content of composition (a1) ranges from 70 to 90% by weight.

The styrenic block copolymers with an elastomer block, in particular of the SI and SIS type, which can be used in composition (a1) are commercially available, often in the form of triblock/diblock mixtures.

Europrène ^® Sol T 166, available from Polimeri Europa (Italy) is a mixture consisting, respectively, of 90% and 10% of SBS triblock (M _w approximately 121 kDa) and of SB diblock (M _w approximately 64 kDa), each of these copolymers having about 30% styrene.

^Solprene® 1205, available from Dynasol, is an SB diblock copolymer (M _w approximately 100 kDa) containing approximately 30% styrene.

Kraton ^® D1183 PT, available from the company Kraton, is a mixture consisting, respectively, of 62% and 38% of SIS triblock and of SI diblock, having approximately 16% styrene.

^Kraton® D1118, available from the company Kraton, is a mixture consisting, respectively, of 22% and 78% of SBS triblock and SB diblock, having approximately 33% styrene.

According to a preferred variant, the HMPSA composition comprises from 25 to 45% by weight of the composition (a1) of styrene block copolymers, and even more preferably from 31 to 40% by weight.

Tackifying resins (a2) :

The HMPSA composition comprises from 35 to 65% by weight of one or more tackifying resins (a2).

• (i) les colophanes d'origine naturelle ou modifiées, telles que par exemple la colophane extraite de la gomme de pins, la colophane de bois extraite des racines de l'arbre et leurs dérivés hydrogénés, deshydrogénés, dimérisés, polymérisés ou estérifiés par des monoalcools ou des polyols comme le glycérol ;
• (ii) des résines obtenues par hydrogénation, polymérisation ou copolymérisation (avec un hydrocarbure aromatique) de mélanges d'hydrocarbures insaturés ayant environ 5, 9 ou 10 atomes de carbone issus de coupes pétrolières ;
• (iii) des résines terpéniques résultant généralement de la polymérisation d'hydrocarbures terpéniques comme par exemple le mono-terpène (ou pinène) en présence de catalyseurs de Friedel-Crafts, éventuellement modifiées par action de phénols ;
• (iv) des copolymères à base de terpènes naturels, par exemple le styrène/terpène, l'alpha-méthyl styrène/terpène et le vinyl toluène/terpène.

The tackifying resin(s) (a2) that can be used have weight-average molar masses M _w generally between 300 and 7000 Da and are chosen in particular from:

• (i) rosins of natural or modified origin, such as for example rosin extracted from pine gum, wood rosin extracted from tree roots and their hydrogenated, dehydrogenated, dimerized, polymerized or esterified derivatives monoalcohols or polyols such as glycerol;
• (ii) resins obtained by hydrogenation, polymerization or copolymerization (with an aromatic hydrocarbon) of mixtures of unsaturated hydrocarbons having approximately 5, 9 or 10 carbon atoms derived from petroleum cuts;
• (iii) terpene resins generally resulting from the polymerization of terpene hydrocarbons such as, for example, mono-terpene (or pinene) in the presence of Friedel-Crafts catalysts, optionally modified by the action of phenols;
• (iv) copolymers based on natural terpenes, for example styrene/terpene, alpha-methyl styrene/terpene and vinyl toluene/terpene.

The tackifying resin or resins (a2) have a softening temperature generally between 5 and 150°C.

The softening temperature (or point) of the tackifying resins that can be used in the composition according to the invention can vary from 5 to 140°C. The softening temperature is determined in accordance with the standardized ASTM E 28 test, the principle of which is as follows. A brass ring with a diameter of approximately 2 cm is filled with the resin to be tested in the molten state. After cooling to room temperature, the ring and the solid resin are placed horizontally in a thermostatically controlled glycerin bath, the temperature of which may vary by 5° C per minute. A steel ball approximately 9.5 mm in diameter is centered on the solid resin disk. The softening temperature is—during the phase of heating up the bath at a rate of 5° C. per minute—the temperature at which the resin disk flows from a height of 25.4 mm under the weight of the ball.

According to a preferred embodiment, the tackifying resin(s) used have a softening temperature of between 80 and 120°C, even more preferably between 90 and 110°C.

• famille (i) : Sylvalite^® RE 100S de la société Arizona Chemical (ester de collophane et de pentaérythritol ayant une température de ramollissement d'environ 100°C ;
• famille (ii) : Escorez^® 2203LC de la société ExxonMobil Chemical, ayant une température de ramollissement d'environ 93°C.

Tackifying resins are commercially available, and mention may be made, for example, of the families above of the following products:

• family (i): ^Sylvalite® RE 100S from the company Arizona Chemical (ester of rosin and pentaerythritol having a softening point of approximately 100° C.;
• family (ii): Escorez® ^2203LC from ExxonMobil Chemical, having a softening temperature of about 93°C.

According to a preferred variant, the HMPSA composition comprises from 40 to 60% of tackifying resins (a2), even more preferably from 40 to 55% by weight.

Plasticizer (a3) :

The HMPSA composition comprises from 7 to 25% by weight of a plasticizer (a3) which consists of a composition (a3) comprising a stand oil (a3-1) of a vegetable oil.

The stand oil (a3-1) of vegetable oil (also called "standoil" in English) is obtained by a process which comprises a step of heating said vegetable oil in the absence of oxygen at a temperature above 200 ° C, preferably greater than 270°C, and even more preferably between 270°C and 360°C.

It is generally accepted that this heating causes a thermal polymerization reaction of the oil, which involves in particular the polymerization of the double bonds and the crosslinking of the corresponding triglycerides, which has the effect of increasing the viscosity of said oil. This reaction is often referred to as the "standolization reaction".

The heating of the vegetable oil is maintained for a time corresponding to the obtaining for the stand oil (a3-1) of a Brookfield viscosity, measured at 20° C., greater than or equal to 50 mPa.s, preferably to 100 mPa.s. Said viscosity is generally less than 100 Pa.s, preferably less than 60 Pa.s.

According to a preferred variant, the stand oil (a3-1) is a stand oil of a vegetable oil whose derived fatty acids comprise a proportion of at least 75% of fatty acids including from 16 to 22 carbon atoms, said proportion being expressed as a percentage by weight based on the total weight of fatty acids derived from said oil.

A vegetable oil is a composition of triple esters of fatty acids and glycerol (also called "triglycerides"). It is obtained from the seeds of plants and of course many vegetable oils are widely available commercially.

The expression “fatty acids derived from vegetable oil” is thus intended to designate the fatty acids present in the molecular structure of these triglycerides. Said fatty acids can be obtained, in the form of isolated compounds, by saponification, hydrolysis or methanolysis of said triglycerides.

The proportion of fatty acids including 16 to 22 carbon atoms is more preferably at least 80% by weight, and even more preferably at least 85% by weight, based on the total weight of fatty acids derived vegetable oil.

According to a very particularly preferred variant, the stand oil (a3-1) is a stand oil of a vegetable oil chosen from sunflower, rapeseed, linseed and soybean oil.

According to one embodiment, the vegetable oil stand oil (a3-1) is a soybean oil stand oil, the Brookfield viscosity of which, measured at 20° C., is greater than or equal to 200 mPa.s, preferably comprised in the range from 0.2 to 9 Pa.s, particularly in the range from 0.2 to 5 Pa.s.

According to another embodiment, the vegetable oil stand oil (a3-1) is a linseed oil stand oil, the Brookfield viscosity of which, measured at 20° C., is greater than or equal to 100 mPa.s, and of preferably within the range from 0.1 to 60 Pa.s, particularly within the range from 2 to 10 Pa.s.

• comme standolie de soja, le Veopol^® 315002 dont la viscosité Brookfield à 20°C est de 267 mPa.s et le Veopol^® 215035 dont la viscosité Brookfield à 20°C est de 4420 mPa.s;
• comme standolie de lin, le Veopol^® 212055 dont la viscosité Brookfield à 20°C est de 5870 mPa.s.

Stand oils are commercially available, and we can cite for example:

• as soybean stand oil, Veopol ^® 315002 whose Brookfield viscosity at 20° C. is 267 mPa.s and Veopol ^® 215035 whose Brookfield viscosity at 20° C. is 4420 mPa.s;
• as flax stand oil, ^Veopol® 212055, the Brookfield viscosity of which at 20° C. is 5870 mPa.s.

These products are available from Vandeputte.

According to a preferred variant, the composition (a3) which can be used as a plasticizer consists of one (or more) stand oil (a3-1).

According to another variant, the composition (a3) which can be used as a plasticizer comprises, in addition to a stand oil (a3-1), a vegetable oil (a3-2) which is chosen from sunflower, rapeseed, linseed and soybean oil. and whose derived fatty acids comprise a proportion of at least 75% of fatty acids including from 16 to 22 carbon atoms, said percentage being a percentage by weight expressed on the basis of the total weight of fatty acids derived from vegetable oil (a3-2). The vegetable oil (a3-2) can be identical to or different from the vegetable oil from which the stand oil (a3-1) is obtained.

In accordance with this last variant, the composition (a3) comprises from 50 to 100% of the stand oil (a3-1) and from 0 to 50% of the vegetable oil (a3-2), these percentages being percentages by weight expressed based on the total weight of the composition (a3).

The proportion of fatty acids including from 16 to 22 carbon atoms in the total weight of fatty acids derived from vegetable oil (a3-2) is preferably at least 80% by weight, and even more preferably at least less than 85% by weight.

According to a preferred variant, the HMPSA composition comprises from 7 to 20% by weight of plasticizer (a3), and more preferentially from 10 to 19%, and even more preferentially from 10% to 15%.

Stabilizers (a4) :

According to a preferred embodiment, the HMPSA composition additionally comprises from 0.1 to 2% of one or more stabilizers (or antioxidant) (a4).

These compounds are introduced to protect said composition from degradation resulting from a reaction with oxygen which is likely to form by the action of heat, light or residual catalysts on certain raw materials such as tackifying resins . These compounds may include primary antioxidants that scavenge free radicals and are generally substituted phenols such as Irganox ^® 1010 from BASF. The primary antioxidants can be used alone or in combination with other antioxidants such as phosphites such as ^Irgafos® 168 also from BASF, or even with UV stabilizers such as amines.

Wax (a5) :

The HMPSA composition according to the invention may also include a wax (a5) of a polyethylene homopolymer (such as AC ^® 617 from Honeywell) or of a copolymer of polyethylene and vinyl acetate. The corresponding amount can be up to 5%.

Finally, it may optionally include pigments, dyes or fillers.

• de 25 à 45 % en poids de la composition (a1) de copolymères à bloc styrénique ;
• de 40 à 60 % en poids de la ou des résines tackifiantes compatibles (a2) ; et
• de 7 à 20 % en poids du plastifiant (a3).

According to a preferred variant, the HMPSA composition comprises, and preferably consists essentially of:

• from 25 to 45% by weight of composition (a1) of styrene block copolymers;
• from 40 to 60% by weight of the compatible tackifying resin(s) (a2); and
• from 7 to 20% by weight of the plasticizer (a3).

• de 31 à 40 % en poids de la composition (a1) de copolymères à bloc styrénique ;
• de 40 à 55 % en poids de la ou des résines tackifiantes compatibles (a2) ; et
• de 10 à 19 % en poids du plastifiant (a3).

According to an even more preferred variant, the HMPSA composition comprises, and preferably consists essentially of:

• from 31 to 40% by weight of composition (a1) of styrenic block copolymers;
• from 40 to 55% by weight of the compatible tackifying resin(s) (a2); and
• from 10 to 19% by weight of the plasticizer (a3).

The viscosity of the HMPSA composition, measured by a Brookfield® ^RVT viscometer at 163° C., is between 4 and 50 Pa.s, preferably between 10 and 40 Pa.s. Such a viscosity is particularly well suited to the nozzles implemented in the industrial units of the coaters for its coating on a printable support layer.

The self-adhesive hot-melt composition according to the invention is prepared by simple mixing of its components at a temperature of between 130 and 200° C., until a homogeneous mixture is obtained. The required mixing techniques are well known to those skilled in the art.

• une couche adhésive (A) constituée de la composition HMPSA objet de l'invention;
• une couche support (B) adjacente à la couche adhésive (A) ; et
• une couche protectrice anti-adhérente (C), adjacente à la couche adhésive (A).

The present invention secondly relates to a multilayer system comprising:

• an adhesive layer (A) consisting of the HMPSA composition which is the subject of the invention;
• a support layer (B) adjacent to the adhesive layer (A); and
• a non-stick protective layer (C), adjacent to the adhesive layer (A).

Adhesive layer (A) :

According to a preferred variant of the multilayer system according to the invention, the thickness of the adhesive layer (A) is strictly greater than 10 μm, preferably comprised within a range ranging from 11 to 100 μm, more preferentially from 12 to 35 μm.

Backing layer (B) :

The support layer (B) included in the multilayer system according to the invention is adjacent to the adhesive layer (A).

According to a more preferred variant of the invention, said layer (B) consists of paper or of a film comprising one or more homogeneous layers of a polymer.

Among the suitable polymers, mention may be made of polyolefins, such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene and linear ultra low density polyethylene, polypropylene and polybutylenes; polystyrene; natural or synthetic rubber; vinyl copolymers, such as polyvinyl chloride, plasticized or unplasticized, and poly(vinyl acetate); olefin copolymers, such as ethylene/methacrylate copolymers, ethylene/vinyl acetate copolymers, acrylonitrile/butadiene/styrene copolymers, and ethylene/propylene copolymers; acrylic polymers and copolymers; polyurethanes; polyethers; polyesters; and mixtures thereof.

Preferably, the support layer (B) is based on acrylic polymers, polyethylene (PE), oriented, non-oriented or bi-oriented polypropylene (PP), polyimide, polyurethane, polyester such as polyethylene terephthalate (PET).

According to yet another variant, the support layer (B) is a printable support layer.

Non-stick protective layer (C) :

The protective non-stick layer (C) can be easily removed without modifying the layer (A) which remains attached to the support layer (B).

According to a preferred variant, said layer (C) comprises a silicone-based material, said material either constituting said layer (C), or present in the form of a surface coating of said layer (C), said coating being intended to be in contact with the adhesive layer (A).

According to a preferred variant of the multilayer system according to the invention, said system is packaged in the form of a winding around a reel (or roll) whose dimensions can vary over a wide range. So, the diameter of such a roll can be from 0.25 to 1 m, and its width is from 0.25 to 2 m.

In accordance with this preferred variant, the protective release layer (C) consists of the support layer (B) included in the multilayer system, in which the face which is opposite to the face in contact with the adhesive layer (A) is coated with a silicone-based material. Such a multilayer system in which the protective release layer (C) is not separate from the layer (B) is sometimes referred to as English of "linerless". Said packaging is particularly advantageous, due to its simplicity and the resulting economy, for converters who convert these roll stocks into final self-adhesive articles, such as labels or self-adhesive tapes.

The HMPSA composition is applied in the molten state at a temperature above 130° C. on the support layer (B) in an amount which is strictly greater than 10 g/m ² and which generally ranges from 11 and 100 g /m ² , preferably from 11 to 35 g/m ² , to constitute the adhesive layer (A).

The application is carried out by known coating techniques such as for example of the lip nozzle type (at a temperature of approximately 160 to 180° C.) or of the curtain type (at a temperature of approximately 120 to 180° C.) . The application of the HMPSA by lip nozzle is generally carried out on the non-stick protective layer (C), the assembly then being laminated on the support layer (B) (transfer coating). The application of the HMPSA by curtain-type coating can be carried out directly on the support layer (B), depending on the coating temperature.

The present invention also relates to the use of the multilayer system as defined previously for the manufacture of self-adhesive articles, such as self-adhesive labels and adhesive tapes.

The invention also relates to a self-adhesive label capable of being obtained by transformation of the multilayer system described above. A printable support layer (B) is preferred in this case.

• une étape d'impression sur la couche support imprimable (B), puis
• une étape de découpe du système multicouche de manière à en réduire la largeur, et donc à le reconditionner sur une bobine de largeur réduite, puis
• une étape (qualifiée d'échenillage) d'obtention d'un système multicouche, conditionné sur la bobine de l'étape précédente, dans lequel la couche protectrice anti-adhérente (C), inchangée, est liée à la seule partie de la couche support imprimée qui correspond à la forme et aux dimensions de l'étiquette auto-adhésive adaptées à son utilisation finale. Cette étape consiste donc en la découpe sélective, puis en l'élimination de la partie indésirable de la couche support imprimable (B) et de la couche adhésive (A), ladite partie étant souvent appelée "squelette de l'étiquette".

The transformation process implemented generally includes:

• a step of printing on the printable support layer (B), then
• a step of cutting the multilayer system so as to reduce its width, and therefore to repackage it on a reel of reduced width, then
• a step (qualified as weeding) for obtaining a multilayer system, packaged on the reel of the previous step, in which the anti-adherent protective layer (C), unchanged, is bonded to only part of the layer printed medium that corresponds to the shape and dimensions of the self-adhesive label adapted to its end use. This step therefore consists in the selective cutting, then in the elimination of the undesirable part of the printable support layer (B) and of the adhesive layer (A), said part often being called "label skeleton".

• de verre ;
• d'une matière plastique usuelle choisie parmi le PolyEthylène Téréphtalate (PET), le PolyChlorure de Vinyle (PVC), le PolyEthylène (PE), notamment le PolyEthylène Haute Densité (HDPE), ou encore le PolyPropylène (PP) ; ou
• de carton, tel que par exemple le carton connu sous la dénomination de carton FIPAGO (dénomination provenant de la Fédération Internationale des fabricants de PApiers GOmmés) de grade Kraftliner et grammage 200 g/m².

This last multilayer system is implemented on the packaging lines of the articles to be labelled, such as packaging, by means of automated systems which separate the self-adhesive labels from the protective layer, and fix them on the items to be labelled. The labeled article is preferably a packaging or container consisting of:

• of glass ;
• a usual plastic chosen from PolyEthylene Terephthalate (PET), Polyvinyl Chloride (PVC), PolyEthylene (PE), in particular High Density PolyEthylene (HDPE), or alternatively PolyPropylene (PP); Where
• of cardboard, such as for example the cardboard known under the name of FIPAGO cardboard (name coming from the International Federation of Gummed Paper Manufacturers) of Kraftliner grade and weight of 200 g/m ² .

The following examples are given purely by way of illustration of the invention and cannot be interpreted in such a way as to limit its scope.

Examples A (reference), examples 1 to 6 (according to the invention) and B, C, D (comparative) :

The compositions shown in Table 1 below are prepared by simple hot mixing at 180° C. of the ingredients indicated.

The Brookfield viscosity of these compositions was measured at a temperature of 163°C. The result is shown in Table 2 in mPa.s.

These compositions were also tested according to the tests described below.

Adhesive power: peel test

The adhesive power of the compositions is evaluated by the peel test at 180°C on a plate of a certain substrate, as described in the FINAT test method no. 1, published in the FINAT Technical Manual 6 ^th edition, 2001. FINAT is the international federation of manufacturers and converters of self-adhesive labels.

The principle of this test is as follows. The HMPSA is coated beforehand at a rate of 20 g/m ² on a support layer consisting of a 50 μm thick PET film.

A test piece in the form of a rectangular strip (25.4 mm×175 mm) is cut from the self-adhesive support thus obtained. This specimen is fixed on a plate made of a certain substrate. The assembly obtained is left for 20 min at room temperature. It is then introduced into a pulling device capable of carrying out the peeling or unsticking of the strip at an angle of 180° and with a separation speed of 300 mm per minute. The device measures the force required to peel the tape under these conditions.

The result is expressed in N/2.54 cm and is indicated, together with the nature of the plate substrate, in Table 2.

Immediate stickiness: loop tack test

The immediate stickiness or tack of the compositions is evaluated by the so-called loop tack instant adhesion test (also called “loop tack”), described in FINAT test method No. 9.

The HMPSA is coated beforehand at a rate of 20 g/m ² on a support layer consisting of a PET film 50 μm thick, so as to obtain a rectangular strip 25.4 mm by 175 mm. The 2 ends of this strip are joined to form a loop with the adhesive layer facing outwards. The 2 joined ends are placed in the mobile jaw of a traction device capable of imposing a speed of movement of 300 mm/minute along a vertical axis with the possibility of going and returning. The lower part of the loop placed in a vertical position is first brought into contact with a horizontal plate of a certain substrate of 25 mm by 30 mm over a square area of approximately 25 mm on a side. From this contact, the direction of movement of the jaw is reversed. The immediate tackiness is the maximum value of the force necessary for the loop to completely detach from the substrate plate.

The result is expressed in N/2.54 cm and is indicated, as well as the nature of the substrate of the horizontal plate, in Table 2.

The peel and tack results obtained for Examples 1 to 6 based on a plasticizer consisting of stand oils are globally of the same order as those of Example A, the plasticizer of which is of petroleum origin.

Tableau 2 Mesure et tests Résultats Ex. A (réf.) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. B (comp.) Ex. C (comp.) Ex. D (comp.) Viscosité Brookfield à 163°C (en mPa.s) 13250 33300 27700 22800 15450 32000 15650 14000 13650 8900 Peel sur acier inox. (N/2,54 cm) 15,4 17,7 15,1 13,0 10,3 23,7 25,4 5,6 8,3 17,6 Peel sur HDPE (N/2,54 cm) 15,3 17,2 14,6 13,0 10,4 20,5 17,0 5,4 7,5 7,8 Peel sur PP (N/2,54 cm) 15,7 17,5 14,5 13,4 10,3 22,7 26,0 5,8 7,6 19,0 Peel sur carton Fipago (N/2,54 cm) 10,1 15,3 11,3 8,9 7,0 16,5 3,9 3,4 3,3 4,6 Loop tack sur verre (N/2,54 cm) 32,2 35,5 31,9 29,7 24,2 43,3 47,1 15,7 17,9 25,2 Loop tack sur HDPE (N/2,54 cm) 22,2 13,1 20,1 23,1 23,6 14,9 22,6 15,6 17,5 15,3 Loop tack sur PP (N/2,54 cm) 29,2 35,3 31,5 29,2 23,6 35,0 32,6 16,1 17,4 16,0 Loop tack sur carton Fipago (N/2,54 cm) 8,4 7,8 7,5 7,3 8,1 9,0 3,1 5,9 5,9 8,5 Said results are also significantly improved compared to the results obtained for Examples B, C and D based on vegetable oil.

<b>Table 2</b> Measurement and testing Results Ex. A (ref.) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example B (comp.) Ex. C (comp.) Ex. D (comp.) Brookfield viscosity at 163°C (in mPa.s) 13250 33300 27700 22800 15450 32000 15650 14000 13650 8900 Peel on stainless steel. (N/2.54cm) 15.4 17.7 15.1 13.0 10.3 23.7 25.4 5.6 8.3 17.6 Peel on HDPE (N/2.54cm) 15.3 17.2 14.6 13.0 10.4 20.5 17.0 5.4 7.5 7.8 Peel on PP (N/2.54cm) 15.7 17.5 14.5 13.4 10.3 22.7 26.0 5.8 7.6 19.0 Peel on Fipago cardboard (N/2.54 cm) 10.1 15.3 11.3 8.9 7.0 16.5 3.9 3.4 3.3 4.6 Loop tack on glass (N/2.54 cm) 32.2 35.5 31.9 29.7 24.2 43.3 47.1 15.7 17.9 25.2 Loop tack on HDPE (N/2.54cm) 22.2 13.1 20.1 23.1 23.6 14.9 22.6 15.6 17.5 15.3 Loop tack on PP (N/2.54cm) 29.2 35.3 31.5 29.2 23.6 35.0 32.6 16.1 17.4 16.0 Loop tack on Fipago cardboard (N/2.54 cm) 8.4 7.8 7.5 7.3 8.1 9.0 3.1 5.9 5.9 8.5

Claims (15)

1. An HMPSA composition which comprises, on the basis of the total weight of said composition:

   - from 20% to 50% by weight of a composition (a1) of styrene block copolymers which comprise at least one elastomer block;

   - from 35% to 65% by weight of one or more tackifying resins (a2); and

   - from 7% to 25% by weight of a plasticizer (a3);

   characterized in that the plasticizer (a3) consists of a composition (a3) comprising a stand oil (a3-1) of a vegetable oil.
2. The HMPSA composition as claimed in claim 1, characterized in that the composition (a1) of styrene block copolymers consists, on the basis of its total weight:

   - of 30% to 90% by weight of at least one diblock copolymer chosen from the group comprising SI, SIB, SB, SEB and SEP, and

   - of 10% to 70% by weight of at least one triblock copolymer chosen from the group comprising SIS, SIBS, SBS, SEBS and SEPS;

   the total content of styrene units of said composition (a1) ranging from 10% to 40% by weight on the basis of the total weight of (a1).
3. The HMPSA composition as claimed in either of claims 1 and 2, characterized in that the tackifying resin (a2) is chosen from:

   - (i) rosins of natural origin or modified rosins and derivatives thereof which are hydrogenated, dehydrogenated, dimerized, polymerized or esterified with monoalcohols or polyols;

   - (ii) resins obtained by hydrogenation, polymerization or copolymerization (with an aromatic hydrocarbon) of mixtures of unsaturated hydrocarbons having around 5, 9 or 10 carbon atoms derived from petroleum cuts;

   - (iii) terpene resins resulting from the polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts, which are optionally modified by the action of phenols;

   - (iv) copolymers based on natural terpenes.
4. The HMPSA composition as claimed in one of claims 1 to 3, characterized in that the vegetable oil stand oil (a3-1) is obtained by a process which comprises a step of heating said vegetable oil in the absence of dioxygen at a temperature above 200°C, preferably above 270°C.
5. The HMPSA composition as claimed in claim 4, characterized in that the heating of the vegetable oil is maintained for a time corresponding to the obtaining, for the stand oil (a3-1), of a Brookfield viscosity, measured at 20°C, of greater than or equal to 50 mPa.s.
6. The HMPSA composition as claimed in one of claims 1 to 5, characterized in that the stand oil (a3-1) is a stand oil of a vegetable oil, of which the derived fatty acids comprise a proportion of at least 75% of fatty acids including from 16 to 22 carbon atoms, said proportion being expressed as a percentage by weight on the basis of the total weight of the fatty acids derived from said oil.
7. The HMPSA composition as claimed in one of claims 1 to 6, characterized in that the stand oil (a3-1) is a stand oil of a vegetable oil chosen from sunflower, rapeseed, linseed and soybean oil.
8. The HMPSA composition as claimed in one of claims 1 to 7, characterized in that the composition (a3) which can be used as plasticizer consists of the stand oil (a3-1).
9. The HMPSA composition as claimed in one of claims 1 to 7, characterized in that the composition (a3) which can be used as plasticizer comprises, in addition to the stand oil (a3-1), a vegetable oil (a3-2) which is chosen from sunflower, rapeseed, linseed and soybean oil and of which the derived fatty acids comprise a proportion of at least 75% of fatty acids including from 16 to 22 carbon atoms, said percentage being a percentage by weight expressed on the basis of the total weight of the fatty acids derived from the vegetable oil (a3-2).
10. A multilayer system comprising:

    - an adhesive layer (A) consisting of the HMPSA composition as defined in one of claims 1 to 9;

    - a support layer (B) adjacent to the adhesive layer (A); and

    - a nonstick protective layer (C), adjacent to the adhesive layer (A).
11. The multilayer system as claimed in claim 10, characterized in that the thickness of the adhesive layer (A) is strictly greater than 10 µm, and preferably within a range of from 11 to 100 µm.
12. The multilayer system as claimed in one of claims 1 to 11, characterized in that it is packaged in the form of a winding around a reel.
13. The multilayer system as claimed in claim 12, characterized in that the protective nonstick layer (C) consists of the support layer (B) wherein the face which is opposite the face in contact with the adhesive layer (A) is coated with a silicone-based material.
14. The use of the multilayer system as defined in one of claims 1 to 13, for the manufacture of self-adhesive articles.
15. A self-adhesive label capable of being obtained by conversion of the multilayer system as defined in one of claims 1 to 13.